WO1998014164A2 - Utilisation de copolymeres solubles dans l'eau comme ingredients actifs de produits cosmetiques - Google Patents

Utilisation de copolymeres solubles dans l'eau comme ingredients actifs de produits cosmetiques Download PDF

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Publication number
WO1998014164A2
WO1998014164A2 PCT/EP1997/005354 EP9705354W WO9814164A2 WO 1998014164 A2 WO1998014164 A2 WO 1998014164A2 EP 9705354 W EP9705354 W EP 9705354W WO 9814164 A2 WO9814164 A2 WO 9814164A2
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WIPO (PCT)
Prior art keywords
vinyl
alkyl
units
acid
aromatic
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PCT/EP1997/005354
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German (de)
English (en)
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WO1998014164A3 (fr
Inventor
Manfred Niessner
Claudia Nilz
Peter Hössel
Stephan Kothrade
Axel Sanner
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Basf Aktiengesellschaft
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Priority to DE59706066T priority Critical patent/DE59706066D1/de
Priority to AT97909334T priority patent/ATE209026T1/de
Priority to AU47067/97A priority patent/AU724653B2/en
Priority to JP51622198A priority patent/JP3827732B2/ja
Priority to IL12890197A priority patent/IL128901A0/xx
Priority to US09/269,337 priority patent/US6231876B1/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to CA002266542A priority patent/CA2266542A1/fr
Priority to EP97909334A priority patent/EP0929285B1/fr
Priority to BR9712152-5A priority patent/BR9712152A/pt
Publication of WO1998014164A2 publication Critical patent/WO1998014164A2/fr
Publication of WO1998014164A3 publication Critical patent/WO1998014164A3/fr
Priority to NO19991527A priority patent/NO312333B1/no

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the invention relates to the use of water-soluble copolymers as constituents of cosmetic agents and to cosmetic agents which contain these copolymers.
  • Polymers are widely used in cosmetics and medicine.
  • soaps, creams and lotions for example, they usually serve as formulation aids, e.g. as a thickener, foam stabilizer or water absorbent or also to alleviate the irritating effects of other ingredients or to improve the dermal application of active ingredients.
  • your task in hair cosmetics is to influence the properties of the hair.
  • Conditioners are used to improve dry and wet combability, feel, shine and appearance, as well as to give the hair antistatic properties. Furthermore, they can have a setting effect by forming hydrophobic films on the hair.
  • Water-soluble polymers with polar, frequently cationic functionalities are preferred which have a greater affinity for the structurally determined negative surface of the hair.
  • the structure and mode of action of various hair treatment polymers are described in Cosmetics & Toiletries 103 (1988) 23.
  • Commercially available conditioner polymers are e.g. cationic hydroxyethyl cellulose, cationic polymers based on N-vinylpyrrolidone, acrylamide and diallyldimethylammonium chloride or silicones.
  • No. 4,713,236 describes hair conditioners based on polymers containing vinylamine units.
  • polyvinylamine and its salts, ⁇ -substituted polyvinylamines such as poly ( ⁇ -amino-acrylic acid) or copolymers are mentioned which, in addition to vinylamine, include comonomers such as vinyl alcohol, acrylic acid, acrylamide, maleic anhydride, vinyl sulfonate and 2-acrylamido Contain copolymerized -2-methylpropane sulfonic acid.
  • comonomers such as vinyl alcohol, acrylic acid, acrylamide, maleic anhydride, vinyl sulfonate and 2-acrylamido Contain copolymerized -2-methylpropane sulfonic acid.
  • Vinylpyrrolidone is mentioned as a concrete example of a cyclic amide.
  • Further examples of vinyl monomers are secondary, tertiary and quaternary amines, such as dimethyldiallyl amium chloride, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and the quaternized derivatives thereof.
  • JP 06 122 725 describes powdered N-vinylformamide homo- and copolymers. These polymers are used e.g. as a component of toners, chromatography materials, carriers for immunodiagnostics and fillers for paints and cosmetics. A suitability of these polymers as conditioning agents, in particular as conditioning agents for shampoos, is not described.
  • Hydrolyzed oligomers of N-vinylformamide are known from US 5,373,076. Hypothetical areas of application for these polymers include adhesives, binders, water treatment, paper production, oil and mineral extraction, medicine and personal care.
  • N-vinyl carboxamides are known which are used as water absorbers and thickeners, for example in the cosmetics sector.
  • Copolymers of acrylamide and (meth) acrylic acid which may also contain N-vinylcarboxamides as further monomers, are also used according to DE 34 27 220 as thickeners in cosmetic or pharmaceutical preparations.
  • EP 452 758 describes hydrocarbon-rich gels for dermal cosmetic and medical applications which, in addition to various surfactants, contain a water-soluble polymer, such as e.g. Polyvinylformamide included.
  • R a and R b are H or Ci-Cs-alkyl
  • the comonomer is selected from vinyl ethers, vinyl lactams, vinyl halides, vinyl esters of monobasic, saturated carboxylic acids, (meth) acrylic esters, amides and nitriles, and esters, Anhydrides and imides of maleic acid are known from DE 14 95 692.
  • GB 1,082,016 describes homopolymers of N-vinyl-N-methyl-acetamide or copolymers of this compound with vinyl esters, vinyl ethers, (meth) acrylic esters, amides and nitriles, vinyl compounds derived from maleic and fumaric acid, styrene, butadiene and Vinyl halides and their use in shampoo, setting and hair spray formulations.
  • the object of the present invention is to provide new polymers with improved effectiveness in cosmetic preparations.
  • R 1 and R 2 are independently H, alkyl, cycloalkyl, aryl or aralkyl, and
  • A represents a chemical bond or an alkylene group
  • the radicals R 3 independently of one another are H, alkyl, cycloalkyl, aryl or aralkyl, or, together with the nitrogen atom to which they are attached, an optionally mono- or polysubstituted, five- to seven-membered, heterocyclic, aromatic or non-aromatic Form a ring which optionally contains one or two further heteroatoms selected from 0, N and S, it being possible for the heterocyclic ring to be fused with a further five- or six-membered, aromatic or non-aromatic ring,
  • R 4 represents H, alkyl or aralkyl and the corresponding acid addition salts thereof
  • the copolymers used according to the invention preferably have a weight-average molecular weight in the range from about 10 3 to 10 8 g / mol, preferably about 10 4 to 10 7 g / mol.
  • Alkyl radicals which can be used according to the invention comprise straight-chain or branched, saturated carbon chains having 1 to 12 carbon atoms.
  • the following radicals can be mentioned: Ci-C ⁇ - alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, 2- or 3-methyl-pentyl; and longer chain residues such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl and the one or more branched analogues thereof.
  • Alkylene residues which can be used according to the invention include straight-chain Ci-Cirj-alkylene residues, such as methylene, ethylene, propylene, butylene, pentylene and hexylene, and branched C 1 -C .
  • n-alkylene radicals such as 1, 1-dimethylbutylene, 1, 3-dimethylbutylene, 1, 1-dimethylbutylene, 1, 2-dimethylpentylene and 1, 3-dimethylhexylene.
  • straight-chain alkylene groups with 1 to 6 carbon atoms are preferred.
  • suitable cycloalkyl radicals include, in particular C 3 -C ⁇ 2 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutane tylethyl, cyclopentylethyl, propyl, butyl, - pentyl, hexyl and the like.
  • C 3 -C ⁇ 2 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cycl
  • Aralkyl radicals which are suitable in accordance with the invention include phenyl and naphthyl -CC-C 2 -alkyl radicals, the C 1 -C 2 -alkyl part being defined as indicated above.
  • Preferred aralkyl radicals are phenyl-C 1 -C 6 -alkyl radicals.
  • Aryl radicals suitable according to the invention are, for example, phenyl and naphthyl.
  • Examples of five- to seven-membered N-heterocyclic radicals can be mentioned: five-membered radicals, such as pyrrolyl, pyrrolinyl, pyrrolidinyl; 1,2- and 1,3-0xazolyl, 1,2- and 1,3-thiazolyl; 1,2- and 1,3-0xazolinyl; 1,2- and 1,3-thiazolinyl; 1,2- and 1,3-0xazolidinyl; 1,2- and 1,3-thiazolidinyl; Pyrazolyl, pyrazolinyl, pyrazolidinyl; Imidazolyl, imidazolinyl, imidazolidinyl; 1, 2, 4-triazolyl, 1, 3, 4-triazolyl.
  • five-membered radicals such as pyrrolyl, pyrrolinyl, pyrrolidinyl; 1,2- and 1,3-0xazolyl, 1,2- and 1,3-thiazolyl; 1,2- and 1,3-0xazolinyl; 1,2- and 1,
  • Six-membered groups such as pyridyl and piperidyl; Pyridazinyl, pyrimidinyl, pyrazinyl; Pipazinyl; 1,2-, 1,3- and 1,4-oxazinyl, morpholinyl, 1,2-, 1,3- and 1,4-thiazinyl; 1,2,3-, 1,2,4- and 1,3,4-triazinyl, 1,2,3-, 1,2,4- and 1,3,4-0xadiazinyl, 1,2,3- , 1,2,4- and 1, 3, 4-thiadiazinyl.
  • Seven-membered radicals such as azepinyl, 1,2-, 1,3- and 1,4-diazepinyl, 1,2-, 1,3- and 1,4-oxazepinyl, 1,2-, 1,3- and 1, 4-thiazepinyl.
  • fused heterocyclic radicals are indolyl, indazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl; Quinoline, isoquinolinyl, 1, 2-dihydroquinolinyl; Phthalazinyl, quinazoline, quinoxalinyl; Benzodiazepinyl, Benzoxazepinyl and Benzothiazepinyl.
  • the heterocyclic radicals according to the invention can optionally be substituted by one or more, such as 1, 2 or 3, in particular 1 or 2, substituents.
  • Suitable substituents are selected from alkyl, cycloalkyl, aryl, aralkyl, OH, O-alkyl, O-aryl, SH, S-alkyl, S-aryl, NH 2 , NH-alkyl, NH-aryl, N (alkyl) 2 / optionally in protonated form, N (alkyl) 3 + Z ⁇ , where rin Z represents the residue of an inorganic or organic acid, COOH, CHO, C00-alkyl, CONH 2 , CONH-alkyl, CON (alkyl) 2 , CN and SO 3 H.
  • alkyl, cycloalkyl, aryl and aralkyl have the above indicated meanings.
  • Preferred copolymers contain, as characteristic structural elements, vinylcarboxamide units of the formula I in which R 1 and R 2 independently of one another are H or alkyl.
  • R 1 is particularly preferably H and R 2 is C 1 -C 6 -alkyl.
  • the copolymers according to the invention contain monomers in which A represents a chemical bond or a C 6 -C 6 -alkyl radical, in particular a chemical bond; R 4 represents H or Ci-C ß- alkyl, in particular H; and the radicals R 3 together with the nitrogen atom to which they are attached represent a five- to seven-membered heterocyclically optionally mono- or polysubstituted ring as defined above.
  • Preferred heterocyclic radicals are five- or six-membered aromatic or non-aromatic rings which optionally contain a further heteroatom selected from 0, N and S, preferably N.
  • the heterocyclic ring has one or two, preferably another, substituent.
  • Preferred substituents are C 1 -C 6 -alkyl, -OH, -O-Ci-C ß- alkyl, -O-phenyl, -SH, -S-C ⁇ -C 6 alkyl, -S-phenyl, -NH 2nd , -NH-C ⁇ -C 6 alkyl, -NH-phenyl, -N (-C-C 6 alkyl) 2 , -N (-C-C 6 alkyl) 3 + Z ⁇ , -COOH, -COO- C ⁇ -C 6 alkyl, -C0NH 2 , -CONH-C ⁇ -C 6 alkyl, -CON (C_ . -C 6 alkyl) 2 , -CN and -SO 3 H.
  • Preferred counterions 7r are Cl _ , Br ⁇ , H 2 P0 4 -, SO 4 2 -, NO 3 -, HCOO-, phenyl-S0 3 _ . If the heterocycle has a quaternized nitrogen heteroatom, the counter ion X ⁇ has the meanings given for Z-.
  • Preferred fused heterocycles are benzene fused heterocyclic rings.
  • Preferred examples of monomers of the formula I are N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl-N-ethylformamide, N-vinyl-N-propylformamide, N-vinyl-N-isopropylformamide, N-vinyl -N-butyl-formamide, N-vinyl-N-sec. -butylformamide, N-vinyl-N-tert. -butylformamide, N-vinyl-N-pentylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and N-vinyl-N-ethylacetamide.
  • monomers of the formula II are optionally mono- or polysubstituted N-vinylpyrroles, N-vinylimidazoles, N-vinylimidazolines, N-vinylpyridines, N-vinylpyridazines, N-vinylpyrimidines, N-vinylpyrazines, N-vinylindoles, N- Vinyl indazoles and N-vinyl benzimidazoles.
  • heterocycle functions are in the form of the free bases or neutralized with mineral acids or organic acids or else quaternized, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
  • heterocyclic monomers are selected from imidazole and imidazolium monomers of the following formulas III and IV:
  • R 5 and R 6 are independently selected from H, alkyl, aryl, aralkyl or together represent a benzannellated ring;
  • X represents the residue of an inorganic or organic acid and R 7 represents H, alkyl or aralkyl and the corresponding imidazoline derivatives.
  • Particularly preferred monomers of the formula III are compounds in which R 5 and R 6 independently of one another are H or C 1 -C 6 -alkyl, in particular H.
  • Particularly preferred monomers of the formula IV are compounds in which R 7 is C 1 -C 4 -alkyl or X is Cl or Br.
  • imidazole and imidazoline monomers are N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, N-vinyl-N'methyl -imidazoliumchlo- rid, N-vinyl-N '-ethyl-imidazolium chloride, N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.
  • copolymers containing a) 0.1 to 99.9, preferably 1 to 99, in particular 5 to 95 mol% of N-vinylcarboxamide units of the formula I, b) 0.1 to 99.9, preferably 1 to 99, in particular 5 to 95 mol% of units of the formula II, c) 0 to 99.8, preferably 0 to 98, in particular 0 to 90 mol% of a) and b) different monoethylenically unsaturated monomer units; and d) 0 to 5, preferably 0 to 4, in particular 0 to 3 mol% of monomer units with at least two ethylenically unsaturated double bonds.
  • Examples of monomers c) are vinyl amines and salts thereof, such as Vinylammoniumhalogenide, vinyl alcohol, vinyl formate, Vinyla- acetate, vinyl propionate, vinyl butyrate, N-vinylpyrrolidone, N-vinyl caprolactam, N-vinyl ureas, C ß vinyl ethers, monoethylenically unsaturated C 3 -C 8 - carboxylic acids and dicarboxylic acids and their esters, amides, anhydrides and nitriles, olefins and vinyl aromatics.
  • vinyl amines and salts thereof such as Vinylammoniumhalogenide, vinyl alcohol, vinyl formate, Vinyla- acetate, vinyl propionate, vinyl butyrate, N-vinylpyrrolidone, N-vinyl caprolactam, N-vinyl ureas, C ß vinyl ethers, monoethylenically unsaturated C 3 -C 8 - carboxylic acids
  • Suitable additional ethylenically unsaturated monomers c) are vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, unsaturated C 3 -bis Cs-carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl acetic acid as well as their alkali and alkaline earth metal salts, esters, amides and nitriles, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate and butyl acrylate or glycol or polyglycol esters of ethylenically unsaturated carboxylic acids, where only one OH group of the glycols and polyglycols is esterified, for example hydroxyethyl acrylate, hydroxyethyl methyl methacrylate, hydroxypropyl methacrylate, Hydroxybutyl acrylate
  • Esters of ethylenically unsaturated carboxylic acids with amino alcohols such as, for. B. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylamino propyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate and diethylamyl nobutylacrylate.
  • the basic acrylates are in the form of the free bases, the salts with mineral acids, such as, for example, hydrochloric acid, sulfuric acid and nitric acid, the salts of organic acids, such as formic acid or benzenesulfonic acid, or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable as monomers c) are unsaturated amides such as, for example, acrylamide, methacrylamide and N-alkyl mono- and di-amides with alkyl radicals of 1 to 6 carbon atoms, e.g. N-methyl-acryl amide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (meth) acrylamides, such as. B.
  • C 1 -C 6 vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl pentyl ether and vinyl hexyl ether can be used as monomers c).
  • N-vinylpyrrolidone N-vinylcaprolactam
  • N-vinylurea N-vinylurea
  • substituted N-vinylureas for example N-vinyl-N'-methylurea and N-vinyl-N '-dimethylurea.
  • Monoethylenically unsaturated compounds with sulfo groups can also be used as monomers c), such as, for example, vinyl sulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid or 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and 2-acrylamido-2-methylpropanesulfonic acid.
  • the compounds having acid groups can be in the form of the free acids, the ammonium, alkali metal and alkaline earth metal salts.
  • a further modification of the copolymers can be achieved by copolymerizing 0 to 5 mol% units of monomers d) with at least two ethylenically unsaturated non-conjugated double bonds.
  • Comonomers of this type are usually used as crosslinkers in copolymerizations. The use of these comonomers during the copolymerization increases the molecular weights of the copolymers.
  • Suitable compounds of this type are, for example, methylenebisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, for example glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, di- vinyldioxane, pentaerythritol triallyl ether, pentaallylsucrose, divinyl urea and divinyl ethylene urea.
  • copolymers to be used according to the invention are obtained by a process known from the literature by radical-initiated copolymerization of monomers of the formulas I (monomers a)) and of formula II (monomers b)) and, if appropriate, in the presence of the above-mentioned further monomers c) and / or d) and possibly subsequently partial cleavage of the carbonyl grouping by hydrolysis.
  • Suitable production processes are described, for example, in EP-A-0 071 050, EP-A-0 251 182 and EP-A-0 216 387, to which reference is hereby expressly made.
  • the polymerization can be carried out in the presence or in the absence of an inert solvent or diluent. Since the polymerization in the absence of inert solvents or diluents usually leads to non-uniform polymers, polymerization in an inert solvent or diluent is preferred.
  • Suitable solvents are, for example, those in which the open-chain N-vinylcarboxamides are soluble.
  • inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, tetrahydrofuran, dioxane, water and mixtures of the inert solvents mentioned.
  • the polymerization can be carried out continuously or batchwise. It takes place in the presence of free-radical initiators, which are used in amounts of 0.01 to 20, preferably 0.05 to 10,% by weight, based on the monomers. If necessary, the polymerization can also be carried out solely by the action of high-energy radiation, e.g. Electron rays or UV rays can be initiated.
  • free-radical initiators which are used in amounts of 0.01 to 20, preferably 0.05 to 10,% by weight, based on the monomers.
  • the polymerization can also be carried out solely by the action of high-energy radiation, e.g. Electron rays or UV rays can be initiated.
  • regulators are, for example, organic compounds which contain sulfur in bound form. These include mercapto compounds such as mercaptoethanol, mercaptopropanol, mercapto-butanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercapto, dodecyl mercaptan.
  • allyl compounds such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.
  • the monomers are usually polymerized in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the monomers can be polymerized discontinuously by heating the reaction mixture to the polymerization temperature and then allowing the reaction to proceed. These temperatures are in the range from 40 to 180 ° C., it being possible to work under normal pressure, reduced or else elevated pressure. Polymers with a high molecular weight are obtained if the polymerization is carried out in water. This can be done, for example, for the preparation of water-soluble polymers in aqueous solution, as a water-in-oil emulsion or by the process of reverse suspension polymerization.
  • the polymerization is preferably carried out in a pH range from 4 to 9, in particular from 5 to 8. In many cases it is advisable to work in the presence of buffers, e.g. primary or secondary sodium phosphate.
  • buffers e.g. primary or secondary sodium phosphate.
  • the polymers described above are optionally obtained by partially cleaving the grouping
  • copolymers which can be used according to the invention and which contain a vinylamine or its corresponding ammonium compound as monomer c) from the N-vinylcarboxamide units to form Ain or ammonium groups.
  • the hydrolysis is preferably carried out in water under the action of acids, bases or enzymes, but can also be carried out in the absence of the hydrolysis agents mentioned. Depending on the reaction conditions during the hydrolysis, ie the amount of acid or base, based on the polymer to be hydrolyzed, and the reaction time and temperature, different degrees of hydrolysis are obtained.
  • the hydrolysis is carried out so far that 0.1 to 99.9 mol%, preferably 1 to 99 mol% and 5 to 95 mol% of the carboxamide residues are very particularly preferably hydrolytically cleaved.
  • Acids suitable for hydrolysis are, for example, mineral acids, such as hydrogen halide (gaseous or in aqueous solution), sulfuric acid, nitric acid, phosphoric acid (ortho-, meta- or polyphosphoric acid) or organic acids, e.g. C __- to Cs-carboxylic acids such as formic acid, acetic acid or propionic acid or aliphatic and aromatic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid.
  • the pH is 0 to 5.
  • 0.05 to 1.5 equivalents of acid preferably 0.4 to 1.2 equivalents, are required.
  • metal hydroxides of metals of the first and second main group of the periodic table can be used, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide.
  • ammonia or alkyl derivatives of ammonia e.g. Alkyl or aryl amines, such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, piperidene, pyrrolidine or aniline.
  • the pH is 8 to 14.
  • the bases can be used in the solid, liquid or, if appropriate, also gaseous state, diluted or undiluted.
  • Ammonia, sodium hydroxide solution or potassium hydroxide solution are preferably used.
  • the hydrolysis in the acidic or alkaline pH range takes place at temperatures from 20 to 170 ° C., preferably 50 to 120 ° C. It is complete after about 2 to 8, preferably 3 to 5 hours.
  • a procedure in which the acids or bases are added in aqueous solution has proven particularly useful. After the hydrolysis, i.a. neutralization so that the pH of the hydrolyzed polymer solution is 2 to 8, preferably 3 to 7. Neutralization is necessary if the progress of the hydrolysis of partially hydrolyzed polymers is to be avoided or delayed.
  • the hydrolysis can also be carried out with the aid of enzymes.
  • a further modification of the polymers may occur in such a way that the copolymerized comonomers are also hydrolyzed.
  • vinyl alcohol units are formed from polymerized units of vinyl esters.
  • the polymerized vinyl esters can be completely or partially saponified.
  • the hydrolyzed copolymer comprises, in addition to unchanged vinyl acetate units, vinyl alcohol units and N-vinylcarboxamide and vinylamine units.
  • Units of monoethylenically unsaturated carboxylic acid anhydrides, esters and amides give rise to carboxylic acid units during the hydrolysis.
  • Polymerized, monoethylenically unsaturated carboxylic acids themselves are not changed during the hydrolysis.
  • Carboxylic acid amide and carboxylic acid units can also be formed from polymerized, monoethylenically unsaturated nitriles. The degree of hydrolysis of the copolymerized comonomers can easily be determined analytically.
  • the amine functions can be in the form of the free bases or neutralized with mineral acids or organic acids, such as, for example, formic acid, acetic acid, valeric acid, 2-ethylhexanoic acid, lauric acid, adipic acid, benzoic acid, p-methoxybenzoic acid, lactic acid, citric acid, in salt form .
  • mineral acids or organic acids such as, for example, formic acid, acetic acid, valeric acid, 2-ethylhexanoic acid, lauric acid, adipic acid, benzoic acid, p-methoxybenzoic acid, lactic acid, citric acid, in salt form .
  • alkylating or quaternizing unsubstituted amine groups are also be carried out with the aid of common alkylating agents, such as alkyl halides, e.g. Methyl chloride, methyl bromide, methyl iodide,
  • the reaction can be carried out in an aqueous medium, in inert organic solvents or in mixtures of water with solvents, optionally with phase transfer catalysis.
  • the alkylation and quaternization are preferably carried out in an aqueous medium.
  • the copolymers used according to the invention have molecular weights of 1000 to 10 million, preferably 10,000 to 5 million, which corresponds to K values of about 5 to 300 or 10 to 250, measured on 1% strength aqueous solutions at pH 7 and 25 ° C according to H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932).
  • copolymers described above are used as active ingredients in cosmetic preparations, for example as conditioners for shampoos, hair treatments, lotions, emulsions, rinses, gels, foams and pre- and post-treatment agents for hair coloring and perm, and as hair setting agents and hair styling agents with care properties. They can also be used as thickeners in cosmetics. tic formulations and in cosmetic preparations for oral care.
  • the N-vinylformamide copolymers according to the invention have improved properties in cosmetic formulations. These improvements in properties are most noticeable in shampoo formulations.
  • the copolymers according to the invention are preferably used in commercially available shampoo formulations with sodium or ammonium lauryl ether sulfate as the base surfactant and optionally further cosurfactants, e.g. Alkyl polyglycosides, cocamidopropyl betaines, sulfosuccinic acid esters, sec.
  • the combability of the hair in particular is improved.
  • the hair is given shine, volume and body as well as excellent strength.
  • the shampoos thus have washing, conditioning
  • copolymers according to the invention also show good conditioning and setting effects in hair treatments, lotions, emulsions, rinses and styling agents, such as gels and foams, and in pretreatment and aftertreatment agents for hair coloring and perm, with excellent care properties.
  • copolymers can also be used as conditioning agents and thickeners in skin care products, such as creams, ointments, emulsions and lotions, and for oral care in toothpastes, gels and mouthwashes.
  • the invention thus also relates to cosmetic compositions comprising at least one polymer as defined above in a cosmetic carrier and optionally in combination with other cosmetically active substances.
  • the polymers according to the invention are usually present in the cosmetic compositions in a proportion of about 0.01 to 15% by weight, for example about 0.1 to 10% by weight, based on the total weight of the composition.
  • customary cosmetic carriers such as, for example, surface-active agents, thickeners, gel-forming agents, solubilizers, humectants, binders, blowing agents, polymers, such as, for example, silicones, Sequestering agents, chelating agents, viscosity modifiers, opacifiers, stabilizers, pearlescent agents, dyes, fragrances, organic solvents, preservatives, pH-adjusting agents and, if appropriate, further conditioning agents can be included.
  • copolymer 1 Preparation of copolymer from 90 mol% N-vinylformamide and 10 mol% N-vinyl-N '-methyl-imidazolium chloride (copolymer 1).
  • the K value of the polymer was 104.
  • the determination of the K value is described in H. Fikentscher "Systematics of Celluloses on the Basis of their Viscosity in Solution", Cellulose Chemistry 13 ., (1932) 58-64 and
  • copolymer 1 according to the preparation example was compared with the known copolymers 2 and 3 with regard to its hair conditioning effect.
  • Copolymer 2 (prior art)
  • Copolymer 3 (prior art)
  • Copolymer added amount of combing force decrease [% tel.qel] [regarding Blank]
  • the decrease in combing force is calculated using the following formula:

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Abstract

La présente invention concerne l'utilisation d'un copolymère soluble dans l'eau, comprenant, en tant qu'éléments structurels caractéristiques, a) des unités de carboxamide acrylique de la formule générale (I), où R1 et R2 représentent, indépendamment l'un de l'autre, H, alkyle, cycloakyle, aryle ou aralkyle, et b) des unités de la formule générale (II), où A représente une liaison chimique ou un groupe alkyle, les résidus de R3 représentent, indépendamment les uns des autres, H, alkyle, cylcoalkyle, aryle ou aralkyle ou, ensemble avec l'atome d'azote auquel ils sont liés, un noyau hétérocyclique, aromatique ou non aromatique, éventuellement mono- ou polysubstitué, de cinq à sept éléments, contenant éventuellement un ou deux autres hétéroatomes choisis parmi O, N et S, le noyau hétérocyclique pouvant être annélisé avec un autre noyau aromatique ou non aromatique de cinq à six éléments, et R4 représente H, alkyle ou aralkyle. L'invention porte aussi sur les produits cosmétiques contenant ces copolymères.
PCT/EP1997/005354 1996-09-30 1997-09-29 Utilisation de copolymeres solubles dans l'eau comme ingredients actifs de produits cosmetiques WO1998014164A2 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AT97909334T ATE209026T1 (de) 1996-09-30 1997-09-29 Verwendung wasserlöslicher copolymere als wirkstoffe in kosmetischen formulierungen
AU47067/97A AU724653B2 (en) 1996-09-30 1997-09-29 Use of water-soluble copolymers as active ingredients in cosmetic formulations
JP51622198A JP3827732B2 (ja) 1996-09-30 1997-09-29 化粧品中の作用物質としての水溶性コポリマーの使用
IL12890197A IL128901A0 (en) 1996-09-30 1997-09-29 Use of water-soluble copolymers as active ingredients in cosmetic formulations
US09/269,337 US6231876B1 (en) 1996-09-30 1997-09-29 Use of water-soluble copolymers as active ingredients in cosmetics
DE59706066T DE59706066D1 (de) 1996-09-30 1997-09-29 Verwendung wasserlöslicher copolymere als wirkstoffe in kosmetischen formulierungen
CA002266542A CA2266542A1 (fr) 1996-09-30 1997-09-29 Utilisation de copolymeres solubles dans l'eau comme ingredients actifs de produits cosmetiques
EP97909334A EP0929285B1 (fr) 1996-09-30 1997-09-29 Utilisation de copolymeres solubles dans l'eau comme ingredients actifs de produits cosmetiques
BR9712152-5A BR9712152A (pt) 1996-09-30 1997-09-29 Uso de um copolímero sol·vel em água, e, composição cosmética.
NO19991527A NO312333B1 (no) 1996-09-30 1999-03-29 Anvendelse av vannlöselige kopolymerer som aktive bestanddeler i kosmetiske formuleringer, samt kosmetisk preparat

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DE19640363A DE19640363A1 (de) 1996-09-30 1996-09-30 Verwendung wasserlöslicher Copolymere als Wirkstoffe in kosmetischen Formulierungen
DE19640363.4 1996-09-30

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US8652456B2 (en) 2004-06-21 2014-02-18 Basf Se Aqueous preparations comprising at least one water-soluble or water-dispersible copolymer with cationgenic groups
US10336849B2 (en) 2014-06-26 2019-07-02 Basf Se Copolymer comprising oxazoline monomers and use thereof as crosslinker
US20200069556A1 (en) * 2018-08-31 2020-03-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and amino silicone compounds
US20200069555A1 (en) * 2018-08-31 2020-03-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and polyamine compounds
US11135151B2 (en) * 2018-08-31 2021-10-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and compound having at least one nucleophilic site capable of reacting with the at least one oxazoline functionalized compounds
US11166904B2 (en) * 2018-08-31 2021-11-09 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and carboxyl group-containing polymers

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DE10119338A1 (de) * 2001-04-20 2002-10-24 Clariant Gmbh Verwendung von Copolymerisaten auf Basis von Acrylamidoalkylsulfonsäuren als Verdicker in Zubereitungen enthaltend organische Lösemittel
DE10261197A1 (de) * 2002-12-20 2004-07-08 Basf Ag Wässrige Polymerdispersion
DE10311616A1 (de) * 2003-03-14 2004-09-23 Basf Ag Pfropfpolymerisate und ihre Verwendung
DE10331870A1 (de) * 2003-07-14 2005-02-10 Basf Ag Kosmetische und pharmazeutische Mittel auf Basis von Polyelektrolyt-Komplexen
DE10331865A1 (de) * 2003-07-14 2005-03-24 Basf Ag Wässrige Polymerdispersion und deren Verwendung in der Kosmetik
DE102005034412A1 (de) * 2005-07-22 2007-01-25 Basf Ag Ampholytisches Copolymer, dessen Herstellung und Verwendung
ES2405615T3 (es) * 2005-07-22 2013-05-31 Basf Se Uso de copolímeros anfolíticos aniónicos y catiónicos
FR2926984B1 (fr) * 2008-01-31 2010-04-02 Oreal Composition cosmetique comprenant un copolymere vinylformamide / vinylformamine et un alcoxysilane, ainsi que son utilisation pour le traitement capillaire
FR2926990B1 (fr) * 2008-01-31 2014-05-09 Oreal Composition cosmetique comprenant un copolymere vinylformamide / vinylformamine et une silicone, ainsi que son utilisation pour le traitement capillaire
FR2926981B1 (fr) * 2008-01-31 2013-03-15 Oreal Composition cosmetique comprenant un copolumere vinylformamide/vinylformamine et un polymere cationique
MX2011002354A (es) * 2008-09-03 2011-04-05 Alberto Culver Co Metodos para estilizacion del cabello.
US8529878B2 (en) * 2008-09-03 2013-09-10 Alberto Culver Company Method for strengthening keratinous fibers
EP2331062A2 (fr) * 2008-09-03 2011-06-15 Alberto-Culver Company Procédé de coiffage
US8540975B2 (en) * 2008-09-03 2013-09-24 Alberto Culver Company Hair styling method
EP2331061A2 (fr) * 2008-09-03 2011-06-15 Alberto-Culver Company Procédé de coiffage
US10005854B2 (en) * 2010-10-06 2018-06-26 Ast Products, Inc. Functionalized hydrophilic and lubricious polymeric matrix and methods of using same
FR3002143B1 (fr) * 2013-02-15 2015-02-20 Oreal Composition cosmetique comprenant un copolymere vinylformamide / vinylformamine, un polymere epaississant cellulosique et un tensioactif amphotere ou zwitterionique
DE102019200135A1 (de) * 2019-01-08 2020-07-09 Beiersdorf Ag Zubereitung mit Vinylamine/N-vinylformamide Copolymer beschichteten Siliciumdioxidpartikeln

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Publication number Priority date Publication date Assignee Title
US8652456B2 (en) 2004-06-21 2014-02-18 Basf Se Aqueous preparations comprising at least one water-soluble or water-dispersible copolymer with cationgenic groups
US10336849B2 (en) 2014-06-26 2019-07-02 Basf Se Copolymer comprising oxazoline monomers and use thereof as crosslinker
US20200069556A1 (en) * 2018-08-31 2020-03-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and amino silicone compounds
US20200069555A1 (en) * 2018-08-31 2020-03-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and polyamine compounds
US11129787B2 (en) * 2018-08-31 2021-09-28 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and polyamine compounds
US11135151B2 (en) * 2018-08-31 2021-10-05 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and compound having at least one nucleophilic site capable of reacting with the at least one oxazoline functionalized compounds
US11154488B2 (en) * 2018-08-31 2021-10-26 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and amino silicone compounds
US11166904B2 (en) * 2018-08-31 2021-11-09 L'oreal Cosmetic compositions containing oxazoline functionalized polymers and carboxyl group-containing polymers

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HUP9904147A2 (hu) 2000-04-28
US6231876B1 (en) 2001-05-15
CA2266542A1 (fr) 1998-04-09
DE19640363A1 (de) 1998-04-02
AU724653B2 (en) 2000-09-28
EP0929285B1 (fr) 2001-11-21
JP2001501659A (ja) 2001-02-06
NO312333B1 (no) 2002-04-29
ATE209026T1 (de) 2001-12-15
IL128901A0 (en) 2000-02-17
WO1998014164A3 (fr) 1998-06-18
CN1128610C (zh) 2003-11-26
CN1239421A (zh) 1999-12-22
BR9712152A (pt) 1999-08-31
ZA978692B (en) 1999-03-29
ES2168613T3 (es) 2002-06-16
RU2186559C2 (ru) 2002-08-10
EP0929285A2 (fr) 1999-07-21
DE59706066D1 (de) 2002-02-21
KR20000048713A (ko) 2000-07-25
JP3827732B2 (ja) 2006-09-27
NO991527D0 (no) 1999-03-29
HUP9904147A3 (en) 2001-11-28
NO991527L (no) 1999-05-19
AU4706797A (en) 1998-04-24

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